公开(公告)号：DE1232974B

公开(公告)日：1967-01-26

申请号：DEB0080829

申请日：1965-03-05

Applicant: BASF AG

Inventor： REPPE DR WALTER ,  MAGIN AUGUST

IPC: C07C37/11

公开(公告)号：DE1173458B

公开(公告)日：1964-07-09

申请号：DEB0062191

申请日：1961-04-19

Applicant: BASF AG

Inventor： REPPE DR WALTER ,  MAGIN AUGUST

IPC: C07C69/34 ,  C07C69/52

Abstract: The invention consists of a process for producing a mixture of esters of aliphatic unsaturated dicarboxylic acids, wherein the acid contains 6 to 12 carbon atoms and the alcohol is a C1-C18 alkanol, a C5-C12 cycloalkanol, or a C7 to C10 arylalkanol, by passing acetylene or methylacetylene into the anhydrous alcohol, at 30 to 120 DEG C., or at most containing 5% water, and simultaneously introducing nickel tetracarbonyl and less than the equivalent amount of nickel of an organic or inorganic non-oxidising acid, and discontinuing the supply of acetylene or methyl acetylene before the alkanol is completely used up. Up to 80% of the nickel tetracarbonyl may be replaced by free carbon monoxide. There may also be added to the reaction mixture ligand field complex formers, a large number of which is specified, a halide, or ligand field complex of copper, iron, cobalt, zinc, cadmium, mercury, tin or bismuth and one or more polymerisation inhibitors. The product may be hydrogenated and/or worked up for free acids. The examples relate to the use of ethanol, isopropanol, isobutanol, cyclohexanol.

公开(公告)号：GB889091A

公开(公告)日：1962-02-07

申请号：GB2754459

申请日：1959-08-12

Applicant: BASF AG

Inventor： REPPE WALTER ,  MAGIN AUGUST

IPC: C07F5/02 ,  C10L1/30

Abstract: Polymeric products may be obtained by heating a borine carbonyl [B(R1R2R3)CO]n where n is 1, 2, 3 or 4, R1, R2 and R3 may each represent an alkyl radical of 2 to 18 carbon atoms, a cycloalkyl radical with 5 to 12 carbon atoms or an aralkyl radical, and R1 and R2 may also be hydrogen. Thus dimeric boron alkyl carbonyls may be heated to 150 DEG to 350 DEG C. For example the boron triethyl or boron tri-n-propyl carbonyls are heated at 250 DEG C. for 2 hours giving a polymer of molecular weight 1,200.ALSO:The invention comprises borine carbonyls of the formula [B(R1R2R3)CO]n in which n is one of the numbers 1, 2, 3 or 4, R1, R2 and R3 each represents an alkyl radical with 2 to 18 carbon atoms, a cycloalkyl radical with 5 to 12 carbon atoms, or an aralkyl radical derived from an ethyl radical by substitution of one or more, preferably two, hydrogen atoms by phenyl or toluyl radicals or by substitution of two hydrogen atoms by methyl and phenyl or toluyl radicals, or R1 and/or R2 may also represent hydrogen atoms. The substituted borine carbonyls may be made by allowing diborane, or a hydrocarbon-substituted diborane, an olefinically unsaturated hydrocarbon and carbon monoxide to react on each other in the absence of water, the introduction of the carbon monoxide being effected under increased pressure. The olefine and carbon monoxide may be allowed to act simultaneously or consecutively, in either order, on diborane. Mono-olefines with 2 to 18 carbon atoms, or the corresponding dienes, cycloaliphatic hydrocarbons with 5 to 12 carbon atoms and 1 to 3 double bonds or aralkyl hydrocarbons derived from ethylene by replacement of one or two hydrogen atoms by phenyl or toluyl radicals and possibly alkyl radicals, are suitable reactants. Intermediate products formed by reaction of diborane and the unsaturated hydrocarbon may be separated if desired. Inert solvents may be used, such as saturated aliphatic hydrocarbons, aromatic hydrocarbons, or ethers, or the unsaturated hydrocarbon itself may also act as solvent. The carbon monoxide may be used at pressures of 5 to 500 atmospheres. The reaction of diborane and hydrocarbon proceeds at temperatures of -30 DEG C. to + 100 DEG C., and the subsequent reaction with carbon monoxide, the simultaneous reaction of all three components or the two stage reaction in the opposite sequence, may all be effected at temperatures of 0 DEG C. to 150 DEG C.

公开(公告)号：DE860058C

公开(公告)日：1952-12-18

申请号：DEB0007105

申请日：1942-08-23

Applicant: BASF AG

Inventor： REPPE WALTER DR ,  MAGIN AUGUST

IPC: C07D295/02

公开(公告)号：DE845515C

公开(公告)日：1952-07-31

申请号：DEB0006149

申请日：1943-02-27

Applicant: BASF AG

Inventor： REPPE WALTER DR ,  MAGIN AUGUST

IPC: C07C209/20

公开(公告)号：GB672379A

公开(公告)日：1952-05-21

申请号：GB505650

申请日：1950-02-28

Applicant: BASF AG

Inventor： REPPE WALTER ,  MAGIN AUGUST

IPC: C07C51/14

Abstract: Carboxylic acid amides are prepared by reacting carbon monoxide and ammonia or a primary or secondary non-aromatic amine with a compound containing at least one olefinic linkage at elevated temperature and pressure in the presence of a catalyst consisting of a cyanide of a metal capable of forming a carbonyl or of a mixture of such a cyanide with a cyanide of a mono- or di-valent metal or ammonia or a primary or secondary non-aromatic amine or the complex compound resulting from such a mixture. Suitable catalysts are Belucci-salt, K2Ni(CN)3, and potassium tetracyano nickelate, K2Ni(CN)4 and the corresponding complex salts of other alkali metals such as sodium or lithium, or of alkaline earth metals such as calcium, barium and magnesium or of other bivalent metals such as zinc, cadmium or mercury or of ammonia or primary or secondary non-aromatic amines. Mixtures of nickel cyanides and cyanides of the mono- and divalent metals mentioned above or of nickel cyanide and ammonia or primary or secondary amines may also be used. The catalysts may be used with a carrier, e.g. aluminium oxide, silicic acid gel or pumice stone. Suitable olefinic starting materials are ethylene, propylene, butylene, butadiene, diisobutylene and their homologues and cyclic olefines such as cyclohexene, cyclooctene, terpenes or styrene. Olefines containing substituents, e.g. allyl alcohol, butene-3-ol-2 and butene-2-diol-1.4, unsaturated ethers, e.g. dihydrofurane and olefine carboxylic acids may also be used. Instead of ammonia primary or secondary non-aromatic amines may be used, e.g. mono- or di-methyl-, -ethyl-, propylamine and their homologues, cyclohexylamine, piperidine, pyrrolidine or hexamethylene imine. The preferred temperature is in the range of 100-200 DEG C. and the preferred pressure is in the range 50-200 atmospheres. The reaction may be carried out continuously or in batches. Water or other solvents, e.g. ether, ketones or saturated hydrocarbons may be used. The products may be used for the production of plastics or as intermediates in the preparation of plasticizers, lacquers, resins, textile assistants or tanning agents. In the examples: (a) propionic acid amide is obtained from carbon monoxide, ammonia and ethylene in the presence of nickel cyanide; compounds of formula C7H12N2O2 and C12H19O6N3 are formed as by-products; (b) tetrahydrofurane carboxylic acid amide is obtained from hydrofurane, ammonia and carbon monoxide in the presence of nickel cyanide; ammonium formate, formic acid and tetrahydrofurane carboxylic acid are obtained as by-products; (c) isovaleric acid amide is obtained from hydroquinone, carbon monoxide and ammonia in the presence of nickel cyanide.

公开(公告)号：GB671731A

公开(公告)日：1952-05-07

申请号：GB505450

申请日：1950-02-28

Applicant: BASF AG

Inventor： REPPE WALTER ,  MAGIN AUGUST

IPC: C07C51/14

Abstract: Aliphatic ketones and keto-carboxylic acids are prepared by reacting carbon monoxide and water with acetylenes at elevated temperature and under increased pressure in the presence of a complex cyanide of a metal capable of forming metal carbonyls or in the presence of a mixture of compounds capable of combining with each other to form such a complex cyanide. Preferably the temperature of the reaction is in the range 60-200 DEG C. and the pressure in the range 10 to 40 atmos. Solvents such as organic oxygen-containing solvents miscible with water, e.g. ethers or ketones, or saturated hydrocarbons may be used. The gases may be diluted with nitrogen or methane. Technical gases such as water-gas, generator gas or electric arc acetylene may be used instead of pure gases. Polyketones or polyketo carboxylic acids are formed and also in some cases monoketones, mono- and dicarboxylic acids and esters. Suitable catalysts are, for example, complex cyanides of nickel such as K2[NiCy3] or K2[NiCy4], complex cyanide containing in the cation metals such as sodium, lithium, calcium, barium, magnesium, zinc, cadmium or mercury or containing in the cation the ammonium radical or the radical of an organic amine. The catalyst may be used in solution or suspension or applied to a carrier, e.g. aluminium oxide, silicic acid gel or pumice stone. The most suitable starting materials are the hydrocarbons of the acetylene series, e.g. methyl-, isopropyl-, vinyl- and divinyl-acetylene, phenyl- and diacetylene. Acetylenes containing substituents, e.g. propargyl alcohol, butinol, butinediol, hexainediol, amino di-propines and -butines and carboxylic acids of the acetylene series may also be used. In the example acetylene, water and carbon monoxide are reacted together in the presence of potassium nickel cyanide at elevated temperature and pressure to give polyketo carboxylic acids and small amounts of ketones.